Ether compounds carrying substituted silyl group

ABSTRACT

A compound of the formula: ##STR1## wherein R 1  and R 2  are each phenyl optionally substituted by one selected from the group consisting of C 1  -C 5  alkyl, C 1  -C 5  alkoxy, C 1  -C 5  alkylthio, C 1  -C 5  alkylenedioxy, halogen, nitro, and halogeno-C 1  -C 5  alkoxy; R 3  and R 4  are each C 1  -C 5  alkyl; and Z is N or CH. A method for preparing the compound (I) and a pesticidal formulation containing the same are also provided.

This invention relates to novel ether compounds carrying a substitutedsilyl group which have been found to be particularly effective in thesuppression of pests or undesirable species of insects, to theirpreparation, to their use and to pesticidal formulations containing thenovel compounds.

Japanese Patent Publication (not examined) No. 196803/1984, No.227861/1984, No. 72928/1982 & 154427/1981, and No. 72928/1982, closereferences found, respectively disclose 2,2-dimethyl-phenylethyl benzylethers, 2,2-dimethyl(or diethyl)-2-arylethyl phenoxypyridylmethyl(orpyridyloxybenzyl) ethers, 2-methyl-2-methyl(or ethyl)-2-arylethylphenoxybenzyl ethers, and 2-methyl-2-methyl(or ethyl)-2-arylethylbenzylfurfuryl(or phenylthiobenzyl, benzoylbenzyl or benzylbenzyl)ethers which have pesticidal activity.

The ether compounds of the present invention are those having asubstituted silyl group, and are therefore quite different from thecompounds disclosed in the above references.

According to the present invention there is provided an ether compoundhaving a substituted silyl group represented by the formula (I):##STR2## wherein R¹ and R² are each phenyl optionally substituted by oneselected from the group consisting of C₁ -C₅ alkyl, C₁ -C₅ alkoxy, C₁-C₅ alkylthio, C₁ -C₅ alkylenedioxy, halogen, nitro, and halogeno-C₁ -C₅alkoxy; R³ and R⁴ are each C₁ -C₅ alkyl; and Z is N or CH.

The compound of the invention has an excellent pesticidal activity andno undesirable action to the higher animals, such as fish. Accordingly,the invention also provides a pesticidal formulation which comprises asan active ingredient from 0.1 to 95% by weight of a compound of theformula (I) associated with at least one carrier or diluent therefor.

This invention also provides a method of suppressing undesirable speciesof insects or pests which comprises applying to the locus of the pests acompound of the formula (I).

This invention further provides a process for preparing a compound ofthe formula (I) which comprises either (A) reacting a compound of theformula: ##STR3## with a compound of the formula: ##STR4## or (B)reacting a compound of the formula: ##STR5## with a compound of theformula:

    Y--R.sup.5                                                 (IV)

wherein R⁵ is C₁ -C₅ alkyl; one of V and W is hydroxyl or its metal saltand the other is halogen or reactive ester of hydroxyl; X is metal orhalogen; Y is halogen or reactive ester of hydroxy; R¹, R² R³ R⁴ and Zare as defined above.

The compound of the formula (I) has a chiral center and, therefore, canexist as either one of two possible stereoisomers or a mixture thereof.The invention includes such isomers and mixture thereof.

The term "C₁ -C₅ alkyl" herein employed refers to a straight or branchedsaturated aliphatic hydrocarbon radical such as methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl,neopentyl, tert.-pentyl, or 1-methylisobutyl. Among them methyl andethyl are preferred.

"C₁ -C₅ alkoxy" refers to an alkoxy group containing C₁ -C₅ alkyl moietydefined above and includes methoxy, ethoxy, propoxy, isopropoxy, butoxy,and pentoxy. "C₁ -C₅ alkylthio" refers to an alkylthio group containingC₁ -C₅ alkyl moiety defined above and includes methylthio, ethylthio,propylthio, isopropylthio, butylthio, and pentylthio.

"C₁ -C₅ alkylenedioxy" refers to an alkylenedioxy group containing oneto five carbon atoms, such as methylenedioxy, ethylenedioxy, orpropylenedioxy.

The term "halogen" or "halogeno" refers to fluorine, chlorine, bromine,and iodine.

The term "halogeno-C₁ -C₅ alkoxy" designates an afore-mentioned C₁ -C₅alkoxy arbitrarily substituted by one or more of halogen atoms,preferably not more than three halogen atoms, such as chloromethoxy,bromomethoxy difluoromethoxy, trifluoromethoxy, 1,2-dichloroethoxy, or1,2,2-trichloroethoxy.

A metal salt of a hydroxyl group as used in the process for preparingthe compound (I) of the invention may be an alkali metal salt such assodium or potassium salt, an alkaline earth metal salt such as calciumor barium salt, or a silver salt. A reactive ester of a hydroxyl groupincludes an inorganic acid ester such as sulfate, or phosphate and anorganic acid ester such as methanesulfonate, toluenesulfonate,trifluoromethanesulfonate and oxalate. THe symbol "X" refers to analkali metal such as sodium or potassium, or an alkaline earth metalsuch as calcium or balium.

The process for preparing the compound (I) is detailed below.

METHOD A

The compound (I) of the invention is prepared by condensation of thecompound (II) and the compound (III) described hereinbefore. Whereeither of V in compound (II) and W in compound (III) is hydroxy, thecondensation is generally conducted in the presence of a base. As thebase employed in the reaction, there may be exemplified organic bases,for example, alkali or alkaline earth metal hydroxides such as sodiumhydroxide, potassium hydroxide and barium hydroxide; alkali or alkalineearth metal hydrides such as sodium hydride; alkali or alkaline earthmetal amides such as sodium amide; alkali carbonates such as sodiumcarbonate and postassium carbonate; metal oxides such as barium oxideand silver oxide; and organic bases, for example, trialkyl amines suchas triethylamine; and basic heterocyclic compounds such as2,6-dimethylpyridine. It is often desirable to conduct the reaction inthe presence of a catalyst selected from tetra-n-butylammonium bromide,copper iodide and copper dust.

The reaction is usually conducted in a solvent such as water or anorganic solvent. The former is employed where sodium hydroxide orcarbonate is used as a base and the latter is employed where the base issodium hydride. Illustrative of the organic solvents aretetrahydrofuran, ether, dioxane, acetonitrile, dimethylformamide,dimethylsulfoxide, benzene and toluene.

The reaction temperature is not critical. However, preferabletemperature is between 0° C. and around the boiling point of the solventemployed. The most preferred is from about room temperature to about 80°C.

The starting compound (II) wherein V is halogen may be prepared by theprocess disclosed in Japanese Patent Publicaton No. 4791/1983. Thecompound (II) wherein V is other than halogen may be derived from thecompound (II) wherein V is halogen by processes well known to thoseskilled in the art. For instance, the compound (II) wherein V ishydroxyl is obtained by reacting a corresponding halogeno compound (II)with potassium acetate, and subsequently treating the resulting productwith lithium aluminum hydride.

The staring compounds (III) are known or prepared by processes which areknown or analogous to known processes.

METHOD B

The compound (Ib) of the present invention is prepared by the reactionof the compound (Ia) with the compound (IV).

The reaction is generally carried out in the presence of a strong basewhere X in compound (Ia) is halogen. As the strong base, an alkali metalsuch as sodium metal or an alkyl alakli metal such as butyl lithium isemployed.

The reaction is generally carried out in the presence of a solvent suchas tetrahydrofuran or ethyl ether. Preferable reaction temperatureranges from about -80° C. to around room temperature.

The starting compound (Ia) is prepared by the afore-mentioned method A.

The compound of the invention are useful for the control of pests ofcultivated plants as well as medical or sanitary pests. Such pestsinclude those of Order Lepidoptera (e.g. Spodoptera, Plutella,Adoxophyes, Dendrolinus, etc.), Hemiptera (e.g. Nephotettix, Myzus,Aphis, etc.), Coleoptera (e.g. Periplaneta, Cannosobruchus) and Acarina.Accordingly, a further embodiment of this invention is a method ofcontrolling such undesirable insects or pests using the compound of theinvention. In addition, the invention also provides a pesticidalformulation containing the compound of the invention.

The pesticidal formulations provided by the invention can take the formof emulsifiable concentrates, wettable powders, dusts, granules, oilsolutions and dispersions, fumigations, smokes (e.g. buring orelectro-heated mosquito-repellent incense), non-heated smokes, poisoningbaits, aerosol preparations and the like. The formulations are generallyproduced by mixing between 0.1 and 95% by weight of the compound of theinvention with one or more of suitable solid, liquid or gaseous carrieror adjuvants such as surfactant, dispersing agent, stabilizing agent,wetting agent and spreading agent, etc.

As solid carriers there may be exemplified clays (e.g. kaolin,bentonite, montmorillonite, pyrophyllite, sericite, etc.), talks, andother inorganic minerals (e.g. hydrated silicon dioxide, pumice,diatomaceous earth, sulfur dust, activated carbon, etc.).

Examples of liquid carriers are alcohols (e.g. methyl alcohol), ketons(e.g. acetone, methyl ethyl keton), ethers (ethyl ether, dioxane,cellosolve, tetrahydrofuran), aromatic hydrocarbons (e.g. benzene,toluene, xylene, methylnaphthalene), aliphatic hydrocarbons (e.g.gasoline, kerosene), esters, nitrils, acid amides (e.g.dimethylformamide, dimethylacetamide), halogenated hydrocarbons (e.g.dichloroethane, trichloroethylene, carbon tetrachloride).

Surfactants employed in the formulations are preferably chosen fromamong alkyl sulfates, alkylsulfonates alkylarylsulfonates,polyethyleneglycol ether, and polyalcohol esters.

Illustrative of adhesive and dispersing agents are casein, gelatin,starch, CMC, acacia, alginic acid, lignin sulfonate, bentonite,molasses, polyvinyl alcohol, pine root oil, and agar. Typicalstabilizers are PAP (isopropyl phosphate), TCP (tricresyl phosphate),tall oil, epoxidated oil, various surfactants and various fatty acidsand esters thereof.

As is well understood, the formulations containing an active compound ofthis invention may also include one or more of other pesticidalcompounds as well as antibiotics, herbicides, soil-improving agents andfertilizers.

The amount of the present active compound applied to the locus of pestswill vary with a number of factors, including the way, time, and locusof application, the nature of pest(s) to be controlled, and the crops tobe protected from such pests. In general, however, good results can beachieved at the application rate of 1-500 g/10 are.

The formulation of the invention can be applied to paddy field, corn andvegetable field, orchard, mulberry field, lawn, meadow, forest, flowergarden, housing land and the like.

The following detailed Examples, Preparations and Experiments arepresented by way of illustration of certain specific embodiments of theinvention, wherein the following abbreviations are employed.

TBAB: tetra-n-butylammonum bromide

THF: tetrahydrofuran

DMSO: dimethyl sulfoxide

EXAMPLE 1

Dimethylphenylsilylmethyl 3-phenoxybenzyl ether (Method A) ##STR6##

A mixture of dimethylphenylsilylmethanol (0.33 gram), 50% aqueous sodiumhydroxide solution (1.20 gram), 3-phenoxybenzyl bromide (0.44 gram), andTBAB (0.07 gram) was stirred for 15 hours at room temperature. Thereaction mixture was added with water and extracted with ethyl ether.The ether layer was washed with saturated sodium chloride solution,dried, and evaporated under vacuum to remove the solvent. The residuewas purified by column chromatography over silica gel (20 gram) using asthe eluent n-hexane:ethyl acetate (100:1), to obtain the title compound.Yield 0.32 gram. Physicochemical properties of the product are listed inTable 2.

EXAMPLE 2-42 ##STR7##

A mixture of the compound of the formula (IIa), 50% sodium hydroxidesolution, the compound of the formula (IIIa) and TBTB are allowed toreact with stirring. Following addition of water to the reactionmixture, ethyl ether extraction was conducted. The ether extract waswashed with saturated sodium chloride solution, and the solvent wasremoved by evaporation under vacuum. The resulting crude residue waspurified by column chromatography to obtain the ultimate product (Ic).

Table 1 lists specific products produced by the general method mentionedabove, wherein there are provided the identity of R^(1a) in compound(IIa), and R^(2a) and Z in compound (IIIa); respective amounts ofcompounds (IIa) and (IIIa), 50% sodium hydroxide, and TBAB employed inthe reaction; reaction conditions; chromatographic conditions; yield ofproduct (Ic) based on the starting compound (IIa). Physiocochemicalproperties of the product (Ic), however, are shown in Table 2.

                                      TABLE 1                                     __________________________________________________________________________    Ex-                    Com-                                                                              Com-                  Chromatograph                am-                                                                              Com-                pound                                                                             pound                                                                             50%-    Reaction                                                                           Reaction                                                                           silica                       ple                                                                              pound               IIa IIIa                                                                              NaOH                                                                              TBAB                                                                              Temp.                                                                              Time gel                                                                              n-Hexane:                                                                            Yield              No.                                                                              No. R.sup.1a                                                                              R.sup.2a                                                                           Z  (g) (g) (g) (g) (°C.)                                                                       (hr) (g)                                                                              Ethyl                                                                                (%)tate            __________________________________________________________________________     1  1  H       H    CH 0.33                                                                              0.44                                                                              1.20                                                                              0.07                                                                              RT   15   20 100:1  46                  2  2  H       4-Cl CH 0.17                                                                              0.25                                                                              0.75                                                                              0.04                                                                              80   1    12 100:1  49                  3  3  H       2-Cl CH 0.19                                                                              0.29                                                                              0.85                                                                              0.05                                                                              80   1    14 100:1  46                  4  4  H       3-Cl CH 0.26                                                                              0.37                                                                              1.02                                                                              0.08                                                                              80   1    20 100:1  55                  5  5  H       4-Br CH 0.18                                                                              0.31                                                                              0.80                                                                              0.05                                                                              80   1    15 100:1  50                  6  7  4-Cl    H    CH 0.30                                                                              0.35                                                                              1.20                                                                              0.09                                                                              RT   24   20 100:1  56                  7  8  4-C.sub.2 H.sub.5 O                                                                   4-F  CH 0.33                                                                              0.44                                                                              1.26                                                                              0.10                                                                              RT   24   22 100:1.2                                                                              68                  8  9  4-Cl    3-Cl CH 0.40                                                                              0.52                                                                              1.00                                                                              0.13                                                                              RT   24   30 100:1  59                  9 10  4-C.sub.2 H.sub.5 O                                                                   3-Cl CH 0.32                                                                              0.43                                                                              1.20                                                                              0.09                                                                              RT   23   21 100:1:2                                                                              74                 10 11  4-C.sub.2 H.sub.5 O                                                                   4-NO.sub.2                                                                         CH 0.32                                                                              0.43                                                                              1.20                                                                              0.10                                                                              RT   24   21 100:4  71                 11 12  H       4-F  CH 0.25                                                                              0.38                                                                              1.20                                                                              0.10                                                                              RT   23   20 100:1  64                 12 13  H       4-NO.sub.2                                                                         CH 0.25                                                                              0.40                                                                              1.20                                                                              0.10                                                                              RT   20   18 100:3  59                 13 14  4-C.sub.2 H.sub.5 O                                                                   2-Cl CH 0.35                                                                              0.45                                                                              0.60                                                                              0.11                                                                              RT   24   25 100:1.2                                                                              68                 14 15  4-F     H    CH 0.31                                                                              0.40                                                                              0.67                                                                              0.11                                                                              RT   24   22 100:1  55                 15 16  4-CH.sub.3 O                                                                          4-F  CH 0.33                                                                              0.42                                                                              0.67                                                                              0.11                                                                              RT   24   24 100:1.2                                                                              33                 16 17  4-Cl    4-F  CH 0.41                                                                              0.52                                                                              0.80                                                                              0.14                                                                              RT   23   30 100:1  68                 17 18  4-C.sub.2 H.sub.5 O                                                                   4-Cl CH 0.40                                                                              0.51                                                                              0.76                                                                              0.13                                                                              RT   24   28 100:1.2                                                                              58                 18 19  4-CH.sub.3 O                                                                          H    CH 1.01                                                                              1.18                                                                              3.20                                                                              0.32                                                                              RT   20   65 100:1.2                                                                              46                 19 20  H       4-CH.sub.3 O                                                                       CH 0.28                                                                              0.47                                                                              1.27                                                                              0.11                                                                              RT   24   23 100:1.2                                                                              63                 20 21  4-C.sub.2 H.sub.5 O                                                                   4-CH.sub.3 O                                                                       CH 0.33                                                                              0.45                                                                              1.18                                                                              0.10                                                                              RT   24   24 100:1.8                                                                              52                 21 23  4-Cl    4-CH.sub.3 O                                                                       CH 0.22                                                                              0.32                                                                              0.65                                                                              0.07                                                                              RT   20   15 100:1.2                                                                              54                 22 24  4-CH.sub.3 O                                                                          4-CH.sub.3 O                                                                       CH 0.22                                                                              0.32                                                                              0.65                                                                              0.07                                                                              RT   21   15 100:1.8                                                                              50                 23 25  4-CH.sub.3                                                                            H    CH 0.36                                                                              0.52                                                                              1.20                                                                              0.13                                                                              RT   20   27 100:1  87                 24 26  3-CH.sub.3                                                                            H    CH 0.38                                                                              0.51                                                                              1.20                                                                              0.13                                                                              RT   24   27 100:1  65                 25 27  4-C.sub.2 H.sub.5 O                                                                   H    N  0.29                                                                              0.33                                                                              1.00                                                                              0.09                                                                              RT   16.5 18 100:4  55                 26 28  H       H    N  0.17                                                                              0.26                                                                              0.80                                                                              0.07                                                                              RT   14   13 100:3  59                 27 29  4-Cl    H    N  0.16                                                                              0.19                                                                              0.64                                                                              0.05                                                                              RT   16   11 100:3  56                 28 30  4-CH.sub.3                                                                            H    N  0.12                                                                              0.17                                                                              0.50                                                                              0.04                                                                              RT   24   10 100:3  60                 29 31  4-CH.sub.3 O                                                                          H    N  0.14                                                                              0.16                                                                              0.80                                                                              0.04                                                                              RT   20   10 100:4  52                 30 32  4-F     H    N  0.18                                                                              0.25                                                                              0.80                                                                              0.06                                                                              RT   12   14 100:3  55                 31 33  3-Cl    H    CH 0.40                                                                              0.52                                                                              1.20                                                                              0.13                                                                              RT   20   30 100:1  65                 32 34  3-CH.sub.3 O                                                                          H    CH 0.50                                                                              0.60                                                                              2.00                                                                              0.16                                                                              RT   24   35 100:1.2                                                                              64                 33 35  2-C.sub.2 H.sub.5                                                                     H    CH 0.20                                                                              0.24                                                                              0.82                                                                              0.07                                                                              RT   24   15 100:1  60                 34 36  2-C.sub.2 H.sub.5 O                                                                   H    CH 0.70                                                                              0.79                                                                              2.60                                                                              0.22                                                                              RT   24   45 100:1.2                                                                              70                 35 37  3-C.sub.2 H.sub.5 O                                                                   H    CH 0.30                                                                              0.34                                                                              1.14                                                                              0.09                                                                              RT   24   20 100:1.2                                                                              62                 36 38  4-C.sub.2 H.sub.5 S                                                                   H    CH 0.50                                                                              0.52                                                                              1.77                                                                              0.14                                                                              RT   24   30 100:1.2                                                                              58                 37 39  3,4-OCH.sub.2 O                                                                       H    CH 0.50                                                                              0.56                                                                              1.80                                                                              0.15                                                                              RT   24   33 100:1.8                                                                              64                 38 40  4-(CH.sub.3).sub.2 CHO                                                                H    CH 0.30                                                                              0.32                                                                              1.10                                                                              0.09                                                                              RT   24   20 100:1.2                                                                              55                 39 41  4-CHF.sub.2 O                                                                         H    CH 0.30                                                                              0.31                                                                              1.03                                                                              0.08                                                                              RT   24   20 100:1.2                                                                              58                 40 42  3,4-OCH.sub.2 O                                                                       H    N  0.25                                                                              0.28                                                                              0.95                                                                              0.08                                                                              RT   20   15 100:5  62                 41 43  4-CHF.sub.2 O                                                                         H    N  0.25                                                                              0.26                                                                              0.86                                                                              0.07                                                                              RT   20   15 100:4  60                 42 44  4-(CH.sub.3).sub.2 CHO                                                                H    N  0.25                                                                              0.27                                                                              0.89                                                                              0.07                                                                              RT   20   15 100:4  56                 __________________________________________________________________________

EXAMPLE 43

Dimethyl(4-ethoxyphenyl)silylmethyl 3-phenoxybenzyl ether (Method A)##STR8##

A mixture of dimethyl(4-ethoxyphenyl)silylmethanol (0.22 gram),3-phenoxybenzyl bromide (0.24 gram), TBAB (0.07 gram), potassiumcarbonate (0.40 gram) and water (1.0 gram) was stirred 15 hours at 80°C. After cooling, the reaction mixture was extracted with ethyl ether,and the extract was washed with saturated sodium chloride solution,dried, and evaporated under vacuum to remove the solvent. The residuewas purified by column chromatography over silica gel (13 gram) usingn-hexane:ethyl acetate (100:1.2) as the eluent to obtain the titlecompound. Yield 0.23 gram. Physicochemical properties of the product arelisted in Table 2.

EXAMPLE 44

Dimethyl(4-ethoxyphenyl)silylmethyl 3-phenoxybenzyl ether (Method A)##STR9##

Dimethyl(4-ethoxyphenyl)silylmethanol (0.25 gram), 50% sodium hydride(0.17 gram), and 3-phenoxybenzyl bromide (0.2 gram) were dissolved in 3ml of THF and the resulting mixture was stirred for 2.5 hours at 80° C.After cooling, the mixture was added with ice, diluted with ethyl ether,and washed with saturated sodium chloride solution. The ether layer wasdried and evaporated under vacuum to remove the solvent.

The residue was purified by column chromatography over silica gel (15gram) using n-hexane:ethyl acetate (100:1.2) as the eluent to obtain thetitle compound. Yield 0.32 gram. Physicochemical properties of theproduct are listed in Table 2.

EXAMPLE 45

Dimethylphenylsilylmethyl 3-(4-methylphenoxy)benzyl ether (Method B)##STR10##

Dimethylphenylsilylmethyl 3-(4-bromophenoxy)benzyl ether (0.53 gram) wasdissolved in 3 ml of THF. To the mixture were added 1.0 ml of 1.55Mn-butyl lithium and subsequently 1 ml of methyl iodide with stirring at-78° C. and the stirring was continued for 10 minutes at the sametemperature and for 15 minutes at room temperature. After addition ofwater, the mixture was extracted with ethyl ether. The ether layer waswashed with saturated sodium chloride solution, dried and evaporatedunder vacuum to remove the solvent. The residue was purified by columnchromatography over silica gel (15 gram) using n-hexane:ethyl acetate(100:1) to obtain the title compound. Yield 0.42 gram. Physicochemicalproperties of the product are listed in Table 2.

                                      TABLE 2                                     __________________________________________________________________________                                            Molecular Formula                                                             Elemental Analysis                    Compound                                                                            n.sub.D                                                                            IR(liquid)                                                                            NMR (CDCl.sub.3)                                                                         Mass Spectrum                                                                           Calculated Found                      No.   (Temp.)                                                                            (cm.sup.-1)                                                                           (δ,ppm)                                                                            (B:Base Peak)                                                                           C   H  N                              __________________________________________________________________________     1    1.5686                                                                             3055,2945,2830,                                                                       0.31(6H,s)3.28(2H,                                                                       348(M.sup.+),333,                                                                       C.sub.22 H.sub.24 O.sub.2 Si          (25.6)     2790,1580,1480,                                                                       s,),4.39(2H,s),                                                                          165,135(B)                                                                              74.82                                                                             6.94                                                                             --                                        1245,1210,835,                                                                        6.68-7.63(14H,m)     76.01                                                                             6.97                                                                             --                                        685                                                                 2    1.5743                                                                             3060,2950,2840,                                                                       0.31(6H,s),3.29(2H,                                                                      382(M.sup.+),367,                                                                       C.sub.22 H.sub.23 O.sub.2 ClSi        (26.0)     2795,1575,1480,                                                                       s,),4.41(2H,s),                                                                          165,135(B)                                                                              69.00                                                                             6.05                                                                             --                                        1250,815,720,                                                                         6.84-7.60(13H,m)     67.15                                                                             5.77                                                                             --                                        690                                                                 3    1.5751                                                                             3060,2950,2835,                                                                       0.31(6H,s),3.32(2H,  C.sub.22 H.sub.23 O.sub.2 ClSi        (25.0)     2795,1575,1470,                                                                       s),4.45(2H,s),       69.00                                                                             6.05                                                                             --                                        1445,1260,1250,                                                                       6.70-7.70(13H,m)     69.09                                                                             6.22                                         835,690                                                             4    1.5783                                                                             8070,2960,2850,                                                                        0.32(6H,s),3.33(2H, C.sub.22 H.sub.23 O.sub.2 ClSi        (25.5)     2810,1585,1475,                                                                       s),4.47(2H,s),       69.00                                                                             6.05                                                                             --                                        1255,845,705                                                                          6.62-7.67(13H,m)     65.68                                                                             5.67                                                                             --                              5    1.5861                                                                             3055,2945,2830,                                                                       0.32(6H,s),3.34(2H,  C.sub.22 H.sub.23 O.sub.2 BrSi        (24.6)     2790,1570,1480,                                                                       s),4.47(2H,s),       61.82                                                                             5.42                                                                             --                                        1250,1070,835,                                                                        6.76-7.75(13H,m)     60.98                                                                             5.44                                                                             --                                        690                                                                 6    1.5648                                                                             3020,2975,2845                                                                        0.28(6H,s),1.36(3H,                                                                      392(M.sup.+),377                                                                        C.sub.24 H.sub.28 O.sub.3 Si          (25.6)     2800,1595,1485,                                                                       t,J=7Hz),3.25(2H,s),                                                                     179(B)    73.43                                                                             7.19                                                                             --                                        1250,1115,840,                                                                        3.96(2H,q,J=7Hz),    73.42                                                                             7.21                                                                             --                                        690     4.39(2H,s),6.65-7.46                                                          (13H,m)                                                     7    1.5728                                                                             2950,2840,2790,                                                                       0.28(6H,s),3.28(2H,                                                                      382(M.sup.+),169(B)                                                                     C.sub.22 H.sub.23 O.sub.2 ClSi        (25.5)     1580,1485,1250,                                                                       s),4.42(2H,s),       69.00                                                                             6.05                                                                             --                                        1085,840,690                                                                          6.73-7.54(13H,m)     69.22                                                                             6.14                                                                             --                              8    1.5551                                                                             2970,2835,2795,                                                                       0.29(6H,s),1.39(3H,                                                                      410(M.sup.+),395,                                                                       C.sub.24 H.sub.27 O.sub.3 FSi         (26.2)     1590,1495,1250,                                                                       t,J=7Hz),3.29(2H,s),                                                                     179(B),135                                                                              70.21                                                                             6.63                                                                             --                                        1200,1115,840,                                                                        4.02(2H,q,J=7Hz),    70.26                                                                             6.61                                                                             --                                        690     4.44(2H,s),6.71-7.55                                                          (12H,m)                                                     9    1.5890                                                                             3050,2945,2830,                                                                       0.30(6H,s),3.30(2H,                                                                      401,169(B)                                                                              C.sub.22 H.sub.22 O.sub.2                                                     Cl.sub.2 Si                           (25.7)     2790,1575,1480,                                                                       s),4.45(2H,s),       63.31                                                                             5.31                                                                             --                                        1465,1250,1080,                                                                       6.73-7.63(12H,m)     62.99                                                                             5.67                                                                             --                                        835,800,690                                                        10    1.5702                                                                             3020,2975,2845,                                                                       0.29(6H,s),1.37(3H,  C.sub.24 H.sub.27 O.sub.3 ClSi        (25.8)     2800,1595,1580,                                                                       t,J=7Hz),3.28(2H,s), 67.51                                                                             6.37                                                                             --                                        1470,1245,1115,                                                                       3.98(2H,q,J=7Hz),    67.99                                                                             6.53                                                                             --                                        840,695,675                                                                           4.42(2H,s),6.67-7.50                                                          (12H,m)                                                    11    1.5828                                                                             2975,2845,2800,                                                                       0.31(6H,s)1.37(3H,                                                                       407,179(B)                                                                              C.sub.24 H.sub.27 O.sub.5 NSi         (25.8)     1590,1580,1515,                                                                       t,J=7Hz),3.30(2H,s), 65.88                                                                             6.22                                                                             3.20                                      1485,1340,1250,                                                                       3.95(2H,q,J=7Hz),    66.12                                                                             6.04                                                                             3.37                                      1115,850,750,                                                                         4.45(2H,s),6.69-8.13                                                  685,700 (12H,m)                                                    12    1.5632                                                                             3065,2955,2845,                                                                       0.31(6H,s)3.28(2H,                                                                       366(M.sup.+),351,                                                                       C.sub.22 H.sub.23 O.sub.2 FSi         (25.6)     2795,1585,1500,                                                                       s),4.38(2H,s),                                                                           165(B),135                                                                              72.10                                                                             6.33                                                                             --                                        1485,1260,1205,                                                                       6.43-7.58(13H,m)     70.55                                                                             6.45                                                                             --                                        845,700                                                            13    1.5900                                                                             3065,2950,2845                                                                        0.33(6H,s),3.35(2H   C.sub.22 H.sub.23 NO.sub.4 Si                    2800,1575,1510,                                                                       s),4.48(2H,a),       67.15                                                                             5.89                                                                             3.56                                      1485,1345,1245,                                                                       6.80-8.27(13H,m)     66.89                                                                             6.10                                                                             3.65                                      1110,840,750,                                                                 730,695                                                            14    1.5703                                                                             2965,2840,1590                                                                        0.27(6H,s),1.36(3H,  C.sub.24 H.sub.27 O.sub.3 ClSi        (25.7)     1575,1470,1250,                                                                       t,J=7Hz),3.23(2H,s), 67.51                                                                             6.37                                                                             --                                        1110,840,680                                                                          3.95,(2H,q,J=7Hz),   67.76                                                                             6.39                                                                             --                                                4.38(2H,s),6.66-7.41                                                          (12H,m)                                                    15    1.5594                                                                             3030,2955,2845,                                                                       0.30(6H,s),3.28(2H,                                                                      366(M.sup.+l ),351,                                                                     C.sub.22 H.sub.23 O.sub.2 FSi         (25.6)     2800,1585,1490                                                                        s),4.42(2H,s),                                                                           183(B)    72.10                                                                             6.33                                                                             --                                        1255,1165,1110,                                                                       6.72-7.62(13H,m)     72.29                                                                             6.43                                                                             --                                        850,825,695                                                        16    1.5657                                                                             3060,3010,2950,                                                                       0.28(6H,s),3.26(2H,                                                                      381,165(B)                                                                              C.sub.23 H.sub.25 O.sub.3 FSi         (25.7)     2840,2795,1590,                                                                       s),3.73(3H,s),4.38   69.67                                                                             6.36                                                                             --                                        1495,1485,1445                                                                        (2H,s),6.59-7.49     69.80                                                                             6.53                                                                             --                                        1250,1200,1115,                                                                       (12H,m)                                                               840,780,690                                                        17    1.5675                                                                             3050,2945,2830                                                                        0.30(6H,s),3.27(2H,                                                                      400(M.sup.+),385,                                                                       C.sub.22 H.sub.22 O.sub.2 FClSi       (25.8)     2785,1580,1490                                                                        s),4.41(2H,s),                                                                           199,169(B)                                                                              65.90                                                                             5.53                                                                             --                                        1480,1250,1195,                                                                       6.57-7.54(12H,m)     65.96                                                                             5.67                                                                             --                                        1080,830,800,                                                                 775,690                                                            18    1.5702                                                                             2975,2840,2800,                                                                       0.28(6H,s),1.37(3H,                                                                      411(M.sup.+),179(B)                                                                     C.sub.24 H.sub.27 O.sub.3 ClSi        (25.8)     1590,1485,1245,                                                                       t,J=7(Hz),3.25(2H,s),                                                                              67.51                                                                             6.37                                                                             --                                        830,690 3.97(2H,q,J=7Hz)     67.09                                                                             6.61                                                                             --                                                4.39(2H,s),6.72-7.42                                                          (12H,m)                                                    19    1.5696                                                                             2955,2835,1590,                                                                       0.28(6H,s)3.24(2H,                                                                       378(M.sup.+),363,                                                                       C.sub.23 H.sub.26 O.sub.3 Si          (25.7)     1490,1250,1115,                                                                       s),3.71(3H,s),4.38                                                                       165(B)    72.88                                                                             6.92                                                                             --                                        845,690 (2H,s)6.67-7.50      73.37                                                                             7.03                                                                             --                                                (13H,m)                                                    20    1.5746                                                                             3070,3050,2960,                                                                       0.31(6H,s),3.31(2H,                                                                      378(M.sup.+),363,                                                                       C.sub.23 H.sub.26 O.sub.3 Si          (25.4)     2845,2805,1610,                                                                       s),3.76(3H,s),4.43                                                                       135(B)    72.98                                                                             6.92                                                                             --                                        1590,1505,1240,                                                                       (2H,s),6.56-7.67     72.92                                                                             6.99                                                                             --                                        1210,840,700                                                                          (13H,m)                                                    21    1.5649                                                                             2950,2825,2800,                                                                       0.28(6H,s)1.38(3H,   C.sub.25 H.sub.30 O.sub.4 Si          (25.5)     1595,1500,1250,                                                                       t,J=7Hz),3.28(2H,s), 71.05                                                                             7.16                                                                              --                                       1210,1115,1040,                                                                       3.78(3H,s)4.02(2H,   70.97                                                                             7.20                                                                             --                                        840,690 q,J=7Hz),4.43(2H,s),                                                          6.72-7.55(12H,m)                                           22    1.5682                                                                             3065,3020,2955,                                                                       0.30(6H,s),2.28(3H,                                                                      362(M.sup.+),347,                                                                       C.sub.23 H.sub.26 O.sub.2 Si          (25.3)     2850,2800,1590,                                                                       s),3.27(2H,s),4.39                                                                       135(B)    76.20                                                                             7.23                                                                             --                                        1505,1485,1250,                                                                       (2H,s)6.66-7.63      76.82                                                                             7.38                                                                             --                                        1220,840,730,                                                                         (13H,m)                                                               695                                                                23    1.5643                                                                             2940,2820,2790,                                                                       0.28(6H,s),3.28(2H,  C.sub.23 H.sub.25 O.sub.3 ClSi        (25.7)     1580,1570,1495,                                                                       s),3.78(3H,s),4.42   66.89                                                                             6.10                                                                             --                                        1480,1440,1235,                                                                       (2H,s)6.62-7.58      66.71                                                                             6.17                                                                             --                                        1205,1080,835,                                                                        (12H,m)                                                               800,685                                                            24    1.5496                                                                             2995,2950,2895,                                                                       0.28(6H,s)3.25(2H,   C.sub.24 H.sub.28 O.sub.4 Si          (25.4)     2830,2800,1590,                                                                       s),3.72(6H,s),4.38   70.55                                                                             6.91                                                                             --                                        1500,1240,1110,                                                                       (2H,s),6.63-7.53     70.72                                                                             6.95                                                                             --                                        1030,830,685                                                                          (12H,m)                                                    25    1.5620                                                                             3060,3025,2950,                                                                       0.28(6H,s),2.28(3H,                                                                      362(M.sup.+),347,                                                                       C.sub.23 H.sub.26 O.sub.2 Si                (25.3)                                                                             2840,2795,1585,                                                                       s),3.25(2H,s),4.38                                                                       179(B),149                                                                              76.20                                                                             7.23                                                                             --                                        1485,1250,1215,                                                                       (2H,s),6.65-7.45     76.18                                                                             7.31                                                                             --                                        1110,840,795,                                                                         (13H,m)                                                               690                                                                26    1.5658                                                                             3025,2945,2835,                                                                       0.31(6H,s),2.30(3H,                                              (25.1)                                                                             2795,1580,1485,                                                                       s),3.29(2H,s),4.42                                                    1250,1210,870,                                                                        (2H,s),6.62-7.56                                                      830,690 (13H,m)                                                    27    1.5625                                                                             3025,2980,2850,                                                                       0.34(6H,s),1.39(3H,                                                                      394(M + H).sup.+,378,                                 (25.2)                                                                             2810,1595,1450,                                                                       t,J=7Hz),3.42(2H,s),                                                                     185(B)                                                     1255,1120,850,                                                                        4.04(2H,q,J=7Hz),                                                     695     4.52(2H,s),6.56-7.80                                                          (12H,m)                                                    28    1.5646                                                                             3075,2970,2860,                                                                       0.37(6H,s),3.45(2H,                                                                      334,185(B)                                            (25.8)                                                                             2815,1595,1580,                                                                       s),4.51(2H,s),                                                        1495,1450,1260,                                                                       6.55-7.75(13H,m)                                                      1125,850,700                                                       29    1.5729                                                                             3060,2945,2835,                                                                       0.35(6H,s),3.42(2H,                                                                      383(M.sup.+),367,                                                                       C.sub.21 H.sub.22 NO.sub.2 ClSi             (25.4)                                                                             2790,1585,1570,                                                                       s),4.50(2H,s),                                                                           185(B)    65.69                                                                             5.78                                                                             3.65                                      1485,1440,1250,                                                                       6.54-7.79(12H,m)     64.95                                                                             5.77                                                                             4.11                                      1080,840,800,                                                                 685                                                                30    1.5634                                                                             2950,2850,2800,                                                                       0.34(6H,s),2.32(3H,                                              (25.6)                                                                             1595,1570,1450,                                                                       s),3.38(2H,s),4.45                                                    1255,1110,840,                                                                        (2H,s),6.46-7.71                                                      795,690 (12H,m)                                                    31    1.5674                                                                             2945,2830,1585,                                                                       0.34(6H,s),3.43(2H,                                              (25.7)                                                                             1570,1490,1445,                                                                       s),3.82(3H,s),4.53                                                    1250,1115,845,                                                                        (2H,s),6.58-7.84                                                      690     (12H,m)                                                    32    1.5579                                                                             3055,3020,2950,                                                                       0.34(6H,s),3.39(2H,                                              (25.7)                                                                             2840,2795,1585,                                                                       s),4.47(2H,s),                                                        1570,1490,1440,                                                                       6.50-7.72(12H,m)                                                      1250,1225,1160,                                                               1150,840,685                                                       33    1.5349                                                                             3030,2950,2830,                                                                       0.30(6H,s),3.28(2H,                                                                      382(M.sup.+),367,                                                                       C.sub.22 H.sub.23 O.sub.2 ClSi        (26.0)     1580,1485,1250,                                                                        s),4.42(2H,s),                                                                          199,183(B)                                                                              69.00                                                                             6.05                                                                             --                                        1210,840,780,                                                                         6.71-7.64(13H,m)     71.41                                                                             6.43                                                                             --                             34    1.5690                                                                             3030,2940,2830,                                                                       0.30(6H,s),3.33(2H,                                                                      378(M.sup.+),363,                                                                       C.sub.23 H.sub.26 O.sub.3 Si          (26.0)     1585,1485,1250,                                                                       s),3.79(3H,s),4.47                                                                       165(B),121                                                                              72.98                                                                             6.92                                                                             --                                        870,835,780,                                                                          (2H,s),6.73-7.57     72.92                                                                             6.94                                                                             --                                        690     (13H,m)                                                    35    1.5689                                                                             3030,2950,2830,                                                                       0.36(6H,s),1.20(3H,                                                                      376(M).sup.+,361,                                                                       C.sub.24 H.sub.28 O.sub.2 Si          (25.9)     1575,1475,1440,                                                                       t,J=7Hz),2.73(2H,q,                                                                      271,193,163(B)                                                                          76.55                                                                             7.49                                                                             --                                        1245,1210,1070,                                                                       J=7Hz),3.39(2H,s),   76.45                                                                             7.45                                                                             --                                        835,750,685                                                                           4.49(2H,s),6.70-7.70                                                          (13H,m)                                                    36    1.5621                                                                             3040,2950,2850,                                                                       0.32(6H,s),1.33(3H,                                                                      392(M).sup.+,179(B)                                                                     C.sub.24 H.sub.28 O.sub.3 Si          (25.9)     1580,1480,1430,                                                                       t,J=7Hz),3.40(2H,s), 73.43                                                                             7.18                                                                             --                                        1235,1070,835,                                                                        3.95(2H,q,J=7Hz),                                                     750,685 4.45(2H,s),6.53-7.57                                                          (13H,m)                                                    37    1.5623                                                                             3020,2950,2835,                                                                       0.30(6H,s),1.37(3H,                                                                      392(M).sup.+,377,                                                                       C.sub.24 H.sub.28 O.sub.3 Si          (25.8)     1580,1475,1245,                                                                       t,J=7Hz),3.31(2H,s),                                                                     196,135(B)                                                                              73.43                                                                             7.18                                                                             --                                        830,775,685                                                                           4.01(2H,q,J=7Hz),    73.26                                                                             7.22                                                                             --                                                4.47(2H,s),6.73-7.53                                                          (13H,m)                                                    38    1.5847                                                                             3045,2950,2830,                                                                       0.28(6H,s),1.28(3H,                                                                      408(M).sup.+,393,                                                                       C.sub.24 H.sub.28 O.sub.2 Si          (26.1)     2790,1580,1485,                                                                       t,J=7hz),2.89(2H,q,                                                                      225,195(B)                                                                              70.54                                                                             6.91                                                                             --                                        1250,1210,1075,                                                                       J=7Hz),3.26(2H,s),                                                                       151       71.30                                                                             6.95                                                                             --                                        840,800,685                                                                           4.39(2H,s),6.63-7.47                                                          (13H,m)                                                    39    1.5777                                                                             3050,2955,2850,                                                                       0.27(6H,s),3.31(2H,                                                                      392(M.sup.+),377,                                                                       C.sub.23 H.sub.24 O.sub.4 Si          (26.1)     1590,1485,1235,                                                                       s),4.50(2H,s),5.95                                                                       179(B)    70.37                                                                             6.16                                                                             --                                        1045,840,805,                                                                         (2H,s),6.72-7.47     70.08                                                                             5.99                                                                             --                                        690     (12H,m)                                                    40    1.5590                                                                             2965,2840,1590,                                                                       0.28(6H,s),1.32(6H,                                                                      406(M).sup.+,363,                                                                       C.sub.25 H.sub.30 O.sub.3 Si          (26.0)     1490,1250,1110,                                                                       d,J=7Hz),3.30(2H,s),                                                                     193(B),149                                                                              73.85                                                                             7.44                                                                             --                                        950,840,690                                                                           4.47(2H,s),4.56(1H,  73.99                                                                             7.41                                                                             --                                                hept.,J=7Hz),6.76-7.61                                                        (13H,m)                                                    41    1.5483                                                                             3025,2950,2845,                                                                       0.30(6H,s),3.30(2H,                                                                      414(M.sup.+),399,                                                                       C.sub.23 H.sub.24 O.sub.3 F.sub.2                                             Si                                    (26.1)     1585,1490,1380,                                                                       s),4.44(2H,s),6.45                                                                       201(B),183                                                                              66.64                                                                             5.84                                                                             --                                        1250,1215,1130,                                                                       1H,t,J=74(Hz),       68.06                                                                             6.13                                                                             --                                        1070,1045,840,                                                                        6.75-7.72(13H,m)                                                      690                                                                42    1.5762                                                                             3030,2945,2855,                                                                       0.32(6H,s),3.42(2H,                                                                      394(M + H).sup.+,                                                                       C.sub.22 H.sub.23 NO.sub.4 Si         (25.9)     1590,1570,1485,                                                                       s),4.53(2H,s),5.95                                                                       378,185(B)                                                                              67.15                                                                             5.89                                                                             3.56                                      1440,1230,1110,                                                                       (2H,s),6.59-7.86     67.16                                                                             5.96                                                                             4.26                                      1035,835,800,                                                                         (11H,m)                                                               685                                                                43    1.5439                                                                             3015,2950,2840,                                                                       0.35(6H,s),3.43(2H,                                                                      416(M + H).sup.+,                                                                       C.sub.22 H.sub.23 NO.sub.3                                                    F.sub.2 Si                            (26.1)     1590,1570,1490,                                                                       s),4.52(2H,s),6.53                                                                       400,185(B)                                                                              63.59                                                                             5.58                                                                             3.37                                      1440,1250,1220,                                                                       (1H,t,J=74Hz),       63.67                                                                             5.93                                                                             3.75                                      1125,1040,835,                                                                        6.57-7.81(12H,m)                                                      800,690                                                            44    1.5549                                                                             2965,2845,1590,                                                                       0.34(6H,s),1.34(6H,                                                                      408(M + H).sup.+,                                                                       C.sub.24 H.sub.29 NO.sub.3 Si         (26.2)     1495,1440,1270,                                                                       d,J=7Hz),3.42(2H,s),                                                                     392,272,185                                                                             70.72                                                                             7.17                                                                             3.44                                      1245,1110,950,                                                                        4.52(2H,s),4.58(1H,                                                                      (B)                                                        840,690 hept.,J=7Hz),                                                                 6.56-7.82(12H,m)                                           __________________________________________________________________________

PREPARATION 1 Chloromethyldimethyl(4-ethoxyphenyl)silane ##STR11##

A mixture of 60 ml of THF, p-bromophenetole (9.7 gram) andchloromethyldimethylsilyl chloride (7.3 gram) was cooled in a dryice/acetone bath. To the mixture was dropwise added 33 ml of 1.55Mn-butyl lithium under an argon atmosphere. After stirring the mixturefor additional 15 minutes at -78° C., the stirring was continued at roomtemperature for 30 minutes. The mixture was added with 6 ml of ethylacetate and 30 ml of water, and extracted with ethyl ether. The etherextract was washed with saturated sodium chloride solution, dried, andconcentrated. Distillation of the residue gave 5.5 gram ofchloromethyldimethyl(4-ethoxyphenyl)silane. Physicochemical data of theproduct is listed in Table 3.

PREPARATION 2 ##STR12##

In the same manner as described in Preparation 1, various startingcompounds listed in Table 3 were prepared according to the abovesynthetic schema.

PREPARATION 3 Dimethyl(4-ethoxyphenyl)silylmethanol ##STR13##

A mixture of chloromethyldimethyl(4-ethoxyphenyl)silane (0.55 gram),potassium acetate (0.47 gram) and 3 ml of DMSO was stirred for 1.5 hoursat 90° C. After cooling to room temperature, the reaction mixture wasadded with water and extracted with ethyl ether. The ether extract waswashed with saturated sodium chloride solution, dried, and concentrated.The residue (0.55 gram) was dissolved in 5 ml of ethyl ether. Lithiumaluminum hydride (100 mg) was added to the resulting solution at 0° C.with stirring and the solution was stirred for 2 hours at the sametemperature. After addition of a minimun amount of saturated ammoniumchloride solution, the mixture was dried over anhydrous sodium sulfate,and concentrated. The residue was purified by column chromatography oversilica gel (15 gram) using n-hexane:ethyl acetate (100:30) as the eluentto give the title compound as a white crystal. Yield 0.50 gram.Physicochemical data of the product is given in Table 4.

PREPARATION 4 ##STR14##

In the same manner as described in Preparation 3, other startingcompounds listed in Table 4 were obtained.

                                      TABLE 3                                     __________________________________________________________________________                           Molecular Formula                                                             Elementary Analysis                                              bp°C.                                                                      NMR      Calculated Found                                       R.sup.1b  (mmHg)                                                                            (CDCl.sub.3,δ,ppm)                                                               C   H  Cl  F                                           __________________________________________________________________________    4-C.sub.2 H.sub.5 O                                                                     103 0.38(6H,s),1.40                                                                        C.sub.11 H.sub.17 ClOSi                                          (2) (3H,J=7Hz),2.86                                                                        57.75                                                                             7.49                                                                             15.50                                                                             --                                                        (2H,s),3.97(2H,                                                                        57.76                                                                             7.59                                                                             15.53                                                                             --                                                        q,J=7Hz),6.79                                                                 (2H,d,J=8Hz),7.34                                                             (2H,d,J=8Hz)                                                    4-CHF.sub.2 O                                                                           80-82                                                                             0.43(6H,s),2.90                                                                        C.sub.10 H.sub.13 ClF.sub.2 OSi                                  (1) (2H,s),6.45((1H,                                                                       47.90                                                                             5.23                                                                             14.14                                                                             15.15                                                     t,J=74Hz),7.05                                                                         47.65                                                                             5.17                                                                             14.59                                                                             15.06                                                     2H,d,J=8Hz),7.48                                                              (2H,d,J=8Hz)                                                    4-Cl      93           C.sub.9 H.sub.12 Cl.sub.2 Si                                     (2)          49.32                                                                             5.52                                                                             32.35                                                                             --                                                                 49.56                                                                             5.62                                                                             32.59                                                                             --                                          4-F       62-63        C.sub.9 H.sub.12 ClFSi                                           (1)          53.32                                                                             5.97                                                                             17.49                                                                             9.37                                                               53.79                                                                             6.59                                                                             17.86                                                                             9.51                                        4-CH.sub.3 O           C.sub. 10 H.sub.15 ClOSi                                                      55.93                                                                             7.04                                                                             16.51                                                                             --                                                                 55.07                                                                             6.82                                                                             17.17                                                                             --                                          4-CH.sub.3                                                                              95                                                                            (1)                                                                 3-CH.sub.3                                                                              96                                                                            (1)                                                                 3-CH.sub.3 O  0.41(6H,s),2.94                                                               (2H,s),3.81(3H,s),                                                            6.80-7.45(4H,m)                                                 3-Cl          0.41(6H,s),2.93                                                               (2H,s),7.25-7.77                                                              (4H,m)                                                          2-C.sub.2 H.sub.5                                                                           0.47(6H,s),1.25                                                               (3H,t,J=7Hz),1.76                                                             (2H,q,J=7Hz),3.06,                                                            (2H,s),7.02-7.55                                                              (4H,m)                                                          2-C.sub.2 H.sub.5 O                                                                         0.40(6H,s),1.41                                                               (3H,t,J=7Hz),3.09                                                             (2H,s),4.04(2H,q,                                                             J=7Hz),6.75-7.49                                                              (4H,m)                                                          3-C.sub.2 H.sub.5 O                                                                         0.40(6H,s),1.41                                                               (3H,t,J=7Hz),2.94                                                             (2H,s),4.05(2H,q,                                                             J=7Hz),6.82-7.48                                                              (4H,m)                                                          4-C.sub.2 H.sub.5 S                                                                     95           C.sub.11 H.sub.17 ClSSi                                          (1)          53.95                                                                             7.00                                                                             14.48                                                                             --                                                        53.66    7.10                                                                              14.50                                                                            --                                              4-(CH.sub.3).sub.2 CHO                                                                  70                                                                            (1)                                                                 3,4-OCH.sub.2 O                                                                         87                                                                            (1)                                                                 __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________                           Molecular Formula                                                             Elementary Analysis                                                NMR        Calculated Found                                       R.sup.1b                                                                              mp°C.                                                                      (CDCl.sub.3,δ,ppm)                                                                 C  H   Cl F                                            __________________________________________________________________________    4-C.sub.2 H.sub.5 O                                                                   36-38                                                                             0.31(6H,s),1.32                                                                          C.sub.11 H.sub.18 O.sub.2 Si                                       (1H,brs),1.37(3H,                                                                        62.81                                                                            8.63                                                                              -- --                                                       t,J=7Hz),3.47(2H,                                                                        62.56                                                                            8.77                                                                              -- --                                                       s),3.99(2H,q,J=                                                               7Hz),6.82(2H,d,J=                                                             8Hz),7.38(2H,d,J=                                                             8Hz)                                                              H                      C.sub.9 H.sub.14 OSi                                                          65.00                                                                            8.49                                                                              -- --                                                                  64.92                                                                            8.52                                                                              -- --                                           4-Cl                   C.sub.9 H.sub.13 ClOSi                                                        53.85                                                                            6.53                                                                              17.66                                                                            --                                                                  53.89                                                                            6.65                                                                              17.72                                                                            --                                           4-F                    C.sub.9 H.sub.13 FOSi                                                         58.66                                                                            7.11                                                                              -- 10.31                                                               58.05                                                                            7.63                                                                              -- 10.12                                        4-CH.sub.3 O           C.sub.10 H.sub.16 O.sub.2 Si                                                  61.18                                                                            8.22                                                                              -- --                                                                  60.30                                                                            8.19                                                                              -- --                                           4-CH.sub.3  0.32(6H,s),1.43                                                               (1H,brs),2.33                                                                 (3H,s),3.53(2H,s),                                                            7.17(2H,d,J=8Hz),                                                             7.45(2H,d,J=8Hz)                                                  3-CH.sub.3  0.30(6H,s),1.56                                                               (1H,brs),2.32(3H,                                                             s),3.51(2H,s),                                                                7.13-7.40(4H,m)                                                   3-CH.sub.3 O           C.sub.10 H.sub.16 O.sub.2 Si                                                  61.18                                                                            8.22                                                                              -- --                                                                  60.83                                                                            8.26                                                                              -- --                                           3-Cl                   C.sub.9 H.sub.13 ClOSi                                                        53.85                                                                            6.53                                                                              17.66                                                                            --                                                                  54.76                                                                            6.80                                                                              16.52                                                                            --                                           2-C.sub.2 H.sub.5      C.sub.11 H.sub.18 OSi                                                         67.98                                                                            9.33                                                                              -- --                                                                  67.52                                                                            9.26                                                                              -- --                                           2-C.sub.2 H.sub.5 O    C.sub.11 H.sub.18 O.sub.2 Si                                                  62.81                                                                            8.62                                                                              -- --                                                                  62.61                                                                            8.66                                                                              -- --                                           3-C.sub.2 H.sub.5 O                                                                       0.33(6H,s),0.97                                                               (1H,brs),1.40(3H,                                                             t,J=7Hz),3.55(2H,                                                             s),4.03(2H,q,J=                                                               7Hz),6.75-7.40                                                                (4H,m)                                                            4-C.sub.2 H.sub.5 S    C.sub.11 H.sub.18 OSSi                                                        58.35                                                                            8.01                                                                              -- --                                                                  58.79                                                                            8.02                                                                              -- --                                           4-(CH.sub.3).sub.2 CHO                                                                    0.32(6H,s),0.94                                                               (1H,brs),1.33(6H,                                                             d,J=7Hz),3.53(2H,                                                             s),4.56(1H,hept.,                                                             J=7Hz),6.87(2H,d,                                                             J=8Hz),7.43(2H,                                                               d,J=8Hz)                                                          4-CF.sub.2 HO                                                                             0.34(6H,s),1.06                                                               (1H,brs),3.53(2H,                                                             s),6.43(1H,t,J=                                                               73Hz),7.03(2H,d,                                                              J=8Hz),7.48(2H,d,                                                             J=8Hz)                                                            3,4-OCH.sub.2 O        C.sub.10 H.sub.14 O.sub.3 Si                                                  57.11                                                                            6.66                                                                              -- --                                                                  57.16                                                                            6.66                                                                              -- --                                           __________________________________________________________________________

    ______________________________________                                        Formulation 1 Oil solution                                                    Ingredient       Part by weight                                               ______________________________________                                        Compound (I) of the                                                                            0.5                                                          Invention                                                                     Kerosene         q.s.                                                         ______________________________________                                    

The active ingredient is dissolved in kerosene to make a total volume of100 part by weight.

    ______________________________________                                        Formulation 2 Emulsifiable Concentrate                                        Ingredient       Part by weight                                               ______________________________________                                        Compound (I) of the                                                                            10                                                           invention                                                                     Solpol 3005X ®                                                                             10                                                           (Emulsifing agent)                                                            Xylene           80                                                           ______________________________________                                    

The above ingredients are mixed to make emulsion.

    ______________________________________                                        Formulation 3 Dust                                                            Ingredient       Part by weight                                               ______________________________________                                        Compound (I) of the                                                                             2                                                           invention                                                                     Clay             88                                                           Talk             10                                                           ______________________________________                                    

The above ingredients are uniformly mixed to obtain the dustpreparation.

    ______________________________________                                        Formulation 4 Wettable Powder                                                 Ingredient        Part by weight                                              ______________________________________                                        Compound (I) of the                                                                             30                                                          invention                                                                     Diatomaceous earth                                                                              45                                                          White carbon      20                                                          Sodium lauryl sulfate                                                                            3                                                          Sodium lignin sulfonate                                                                          2                                                          ______________________________________                                    

The above ingredients are uniformly admixed to obtain the wettablepowder preparation.

TEST 1 Samples

The compound of the invention to be tested is dissolved in a minimumamount of DMF. Distilled water containing Tween 20 at the concentrationof 100 ppm is thereto added to prepare a series of samples of thedesired concentrations.

Test Procedure

A. Suppression of Spodoptera litura larvae

Cabbage leaves (5×5 cm) were immersed in the sample solution as preparedabove and air dried. Two leaves were placed in a petri dish (9 cmdiameter) and 10 second-instar larvae of Spodoptera litura were placedin the dish. The dish was held at 25° C. and the mortality of the larvaewas measured after 48 hours.

C. Suppression of Plutella xylostella larvae

Cabbage leaf (5×5 cm) was immersed in the sample solution and air dried.The leaf was placed in a petri dish (9 cm diameter) and 10 third-instarlarvae of Plutella xylostella were placed in the dish. The dish was heldat 25° C. and the mortality of the larvae was measured after 48 hours.

D. Suppression of Adoxophyes sp. larvae

Whole tea leaves were immersed in the sample solution and air dried.Three leaves were placed in a polyethylene petri dish (6 cm diameter, 4cm depth) and 10 forth-instar larvae of Adoxophyes sp. were placed inthe dish. The dish was held at 25° C. and the mortality of the larvaewas measured after 48 hours.

F. Suppression of Nephotettix cincticeps larvae

Six or seven rice seedlings of 1.5 to 2 plant age in leaf number werebundled and the roots were wrapped in sponge. The seedlings were placedin a polyethylene cup (diameter 6 cm, depth 4 cm) and the cup is placedin a rotary application tower, whereby the vegetative parts of theseedlings were sprayed with 2 ml of the sample solution and air dried.The treated seedlings were covered with a transparent plastic cylinderand ten female larvae were placed in the cylinder. The atmosphere in thecylinder was kept at 25° C., and the mortality after 48 hours wasmeasured.

I. Suppression of Myzus persicae larvae

A polyethylene cup (diameter 6 cm, depth 4 cm) was filled with 0.3% agargel and a piece of Chinese cabbage leaf (3×3 cm) was placed on the gel.A no-wing adult of Myzus persicae was placed on the cabbage and allowedto egg-deposit while keeping the surrounding atmosphere at 25° C. for 24hours. After removing the adult, 2 ml of the sample was sprayed on theleaf under a rotary application tower. The test system was kept at 25°C. for 48 hours and the mortality of born larvae was measured.

M. Suppression of Tetranychus cinnabrinus

A polyethylene cup (diameter 6 cm, depth 4 cm) was filled with 0.3% agargel and a piece of bush bean leaf (diameter 2 cm) was placed on the gel.Twelve adults of Tetranychus cinnabrinus were placed on the leaf. After24 hours at 25° C., dead and feeble worms were removed and 2 ml of thesample solution was sprayed on the leaf under a rotary applicationtower. Following such treatment the test system was kept at 25° C. andthe mortality was measured after 48 hours.

O. Suppression of Tetranychus urticae

The same test procedure as above was repeated on Tetranychus urticae.

R. Suppression of Periplaneta americana larvae

A filter paper soaked with the sample solution was placed in a petridish (diameter 9 cm). Five Periplaneta americana larvae within 7 daysafter hatching were placed in the dish hold at 25° C. and the mortalityafter 48 hours was measured.

S. Suppression of Bruchus pisorum

Ten Bruchus pisorum adults within 24 hours after hatching were placed ina screw cylinder (diameter 1.8 cm, height 5 cm) with stainless nets atthe up-and-down openings. The cylinder was submerged in the samplesolution, and the worms exposed to the solution were air dried. THemortality was measured after 48 hours at 25° C.

Test Results

Table 5 shows the test results wherein the mortality (%) of each worm atthe concentration of 250 ppm of each of the indicated compounds (I) isgiven using the following codes:

A: Spodoptera litura (larvae)

C: Plutella xylostella (larvae)

D: Adoxophyes sp. (larvae)

F: Nephotettix cincticeps (larvae)

I: Myzus persicae (larvae)

M: Tetranychus cinnabrinus (adult)

O: Tetranychus urticae (adult)

R: Periplaneta americana (larvae)

S: Bruchus pisorum (adult)

                  TABLE 5                                                         ______________________________________                                        Compound                                                                      No.     A      C      D    F   I    M   O   R    S                            ______________________________________                                         1             80                                                              6      100    100    100                   100   83                           8             90     100                   100  100                           7                    95                    100  100                           9                    100                                                     15                    100                   100  100                          17                    100                   100   77                          33             100    80                                                      25             90     90                         100                          39       90    90     95       100          100                               41      100    100    95       85   83      100                               42             90              97           100                               43      100    80     90       100  94  97  100                               28             80                                                             27      100    70     100  87  83                                             44             100    80            93  69  100                               29       75    85     70       88           100                               40                                  97  86  100                               ______________________________________                                    

TEST 2

This test was conducted using Oryzias latipes (female adult) (wholelength 2.74±0.089 cm, length without tail 2.25±0.069 cm, weight0.199±0.0176 g) according to the method described in Japanese IndustrialStandard K-0102(1). No feed was given to the fish for 48 hours beforetest. Compound No. 1 and No. 27 were dissolved in aqueous DMSO solutionat a given concentration in a glass beaker (3 L). Ten fish were kept inthe beaker at 25.0±0.5° C. The mortality was measured at one hourinterval until 8 hours after treatment, and then 24 hours intervals(total 96 hours). Table 6 lists the test results.

                  TABLE 6                                                         ______________________________________                                                 Concentration                                                                          Mortality                                                   Treatment  (mg/l)     24     48  72   96  (hours)                             ______________________________________                                        Compound No. 1                                                                           100        0      0   0    0                                       Compound No. 27                                                                          100        0      0   0    0                                                  56.2       0      0   0    0                                                  31.0       0      0   0    0                                       ______________________________________                                    

What we claim is:
 1. A compound of the formula: ##STR15## wherein R¹ andR² are each phenyl optionally substituted by one selected from the groupconsisting of C₁ -C₅ alkyl, C₁ -C₅ alkoxy, C₁ -C₅ alkylthio, C₁ -C₅alkylenedioxy, halogen, nitro, and halogeno-C₁ -C₅ alkoxy; R³ and R⁴ areeach C₁ -C₅ alkyl; and Z is N or CH.
 2. A compound according to claim 1wherein R² is phenyl substituted by one selected from the groupconsisting of C₁ -C₅ alkyl, C₁ -C₅ alkoxy, C₁ -C₅ alkylthio, C₁ -C₅alkylenedioxy, halogen, nitro, and halogeno-C₁ -C₅ alkoxy and, R¹, R³,R⁴ and Z are as defined in claim
 1. 3. A compound according to claim 1wherein R¹ is C₁ -C₅ alkylthiophenyl, C₁ -C₅ alkylenedioxyphenyl,nitrophenyl or halogeno-C₁ -C₅ alkoxyphenyl, R² is phenyl, R³, R⁴ and Zare as defined in claim
 1. 4. A compound according to claim 3 wherein R³and R⁴ are each C₂ -C₅ alkyl.
 5. A pesticidal composition comprising asan active ingredient from 0.1 to 95% by weight of a compound of theformula (I) as defined in claim 1 associated with at least one carrieror diluent therefor.
 6. A method of suppressing pests which comprisesapplying to the locus of the pests a compound of the formula (I) asdefined in claim
 1. 7. A process for preparing a compound of the formula(I) as defined in claim 1 which comprises reacting a compound of theformula: ##STR16## wherein Y is hydroxyl or its metal salt and R¹, R³,and R⁴ are as defined above with a compound of the formula: ##STR17##wherein X is halogen, and R² and Z are as defined above.